U.S. patent number 5,495,036 [Application Number 08/304,315] was granted by the patent office on 1996-02-27 for metal (iii) complexes containing conjugated, non-aromatic anionic ii-bound groups and addition polymerization catalysts therefrom.
This patent grant is currently assigned to The Dow Chemical Company. Invention is credited to W. Jack Kruper, Jr., David R. Neithamer, Peter N. Nickias, David R. Wilson.
United States Patent |
5,495,036 |
Wilson , et al. |
February 27, 1996 |
**Please see images for:
( Certificate of Correction ) ** |
Metal (III) complexes containing conjugated, non-aromatic anionic
II-bound groups and addition polymerization catalysts therefrom
Abstract
Novel Group 4, Group 3 or Lanthanide metal complexes wherein the
metal is in the +3 formal oxidation state containing a cyclic or
non-cyclic, nonaromatic, anionic, dienyl ligand group bound to M
and having a bridged ligand structure, catalytic derivatives of
such complexes; and the use thereof as catalysts for polymerizing
addition polymerizable monomers are disclosed.
Inventors: |
Wilson; David R. (Midland,
MI), Neithamer; David R. (Midland, MI), Nickias; Peter
N. (Midland, MI), Kruper, Jr.; W. Jack (Sanford,
MI) |
Assignee: |
The Dow Chemical Company
(Midland, MI)
|
Family
ID: |
23175993 |
Appl.
No.: |
08/304,315 |
Filed: |
September 12, 1994 |
Current U.S.
Class: |
556/12; 502/103;
502/117; 526/127; 534/15; 556/1; 556/52 |
Current CPC
Class: |
C07F
17/00 (20130101); C08F 10/00 (20130101); C08F
10/00 (20130101); C08F 4/6592 (20130101); C08F
4/65908 (20130101); C08F 4/65912 (20130101); C08F
4/6592 (20130101) |
Current International
Class: |
C07F
17/00 (20060101); C08F 10/00 (20060101); C08F
4/00 (20060101); C08F 4/6592 (20060101); C08F
4/659 (20060101); C07F 007/28 () |
Field of
Search: |
;556/52,12,1 ;534/15
;502/103,117 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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277003 |
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Aug 1988 |
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EP |
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416815 |
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Mar 1991 |
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EP |
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468651 |
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Jan 1992 |
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EP |
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514828 |
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Nov 1992 |
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EP |
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520732 |
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Dec 1992 |
|
EP |
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WO9308199 |
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Apr 1993 |
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WO |
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WO9319104 |
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Sep 1993 |
|
WO |
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WO9400500 |
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Jan 1994 |
|
WO |
|
Other References
R D. Ernst, Chem. Rev. 88, 1255-1291 (1988). .
R. D. Ernst, et al., J. Am. Chem. Soc., 107, 5016-5018 (1985).
.
Jutzi, et al., Chem. Ber., 117, 1885-95 (1984). .
J. Am. Chem. Soc., 103, 6788-6789 (1981), T. J. Barton et al. .
Zh. Oshch. Khim., 44, 226-227 (1979) E. A. Chernyshev et
al..
|
Primary Examiner: Nagumo; Mark
Claims
What is claimed is:
1. A metal complex corresponding to the formula: ##STR13## wherein:
M is a Group 3, Group 4 or Lanthanide metal in the +3 formal
oxidation state;
L is a group containing a cyclic or noncyclic, non-aromatic,
anionic, dienyl ligand group bound to M and Z, said L group
containing up to 60 nonhydrogen atoms, and being selected from the
group consisting of 2,4-dimethylpentadienyl-,
1,5-dimethylpentadienyl-, silyl substituted pentadienyl-, silyloxy
substituted pentadienyl-, hydrocarbyloxy substituted pentadienyl-,
cyclohexadienyl-, cyclosilahexadienyl-, cycloheptadienyl-,
cyclooctadienyl-, diphenyl-.eta..sup.5 -methyl-, and
di(1-cyclohexenyl)-.eta..sup.5 -methyl- groups, and inertly
substituted derivatives of such cyclohexadienyl-,
cyclosilahexadienyl-, cycloheptadienyl-, cyclooctadienyl-,
diphenyl-.eta..sup.5 -methyl- and di(1-cyclohexenyl)-.eta..sup.5
-methyl- groups;
Z is a moiety covalently bound to both L and Y, comprising boron,
or a member of Group 14 of the Periodic Table of the Elements, said
moiety having up to 60 non-hydrogen atoms;
Y is a moiety comprising nitrogen, phosphorus, sulfur or oxygen
through which Y is covalently bound to both Z and M, said moiety
having up to 20 nonhydrogen atoms;
X' independently each occurrence is a Lewis base containing up to
nonhydrogen atoms;
X is a monovalent anionic moiety having up to 20 non-hydrogen
atoms, provided however that X is not an aromatic group that is
.pi.-bonded to M and optionally X and one or more X' groups may be
bonded together thereby forming a moiety that is both covalently
bound to M and coordinated thereto by means of Lewis base
functionality; and
q is a number from 0 to 3.
2. A metal complex according to claim 1 wherein L corresponds to
the formula: ##STR14## wherein: R' in each occurrence is a ligand
that is independently selected from the group consisting of
hydrogen, hydrocarbyl, silyl, germyl, siloxy, amino,
hydrocarbyloxy, cyano, halo and combinations thereof, said R'
having up to 20 non-hydrogen atoms, and optionally, two or more R'
groups (where R' is not hydrogen, halo or cyano) may together form
a divalent derivative of one of the foregoing ligands, and provided
further that one R' comprises a covalent bond to Z.
3. A metal complex according to claim 1 wherein L is selected from
the group consisting of divalent derivatives of
2,4-dimethylpentadien-3-yl, cyclohexadienyl, cyclosilahexadienyl,
cycloheptadienyl, and cyclooctadienyl groups; hydrocarbyl, silyl,
hydrocarbyloxy and siloxy substituted derivatives of such groups;
partially hydrogenated anthracenyl, and partially hydrogenated
naphthalenyl groups; and hydrocarbyl, silyl, hydrocarbyloxy or
siloxy substituted derivatives of such partially hydrogenated
anthracenyl and partially hydrogenated naphthalenyl groups.
4. A metal complex according to claim 1 corresponding to the
formula: ##STR15## wherein: Y is --O--, --S--, --NR*--,
---R*--;
Z is SiR*.sub.2, CR*.sub.2, SiR*.sub.2 SiR*.sub.2, CR*.sub.2
CR*.sub.2, CR*.dbd.CR*, CR*.sub.2 SiR*.sub.2, CR*.sub.2 CR*.sub.2
CR*.sub.2, CR*.sub.2 SiR*.sub.2 CR*.sub.2, SiR*.sub.2 CR*.sub.2
CR*.sub.2, SiR*.sub.2 CR*.sub.2 SiR*.sub.2, SiR*.sub.2 SiR*.sub.2
CR*.sub.2, SiR*.sub.2 SiR*.sub.2 SiR*.sub.2, or GeR*.sub.2 ;
wherein:
R* each occurrence is independently hydrogen, or a member selected
from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and
combinations thereof, said R* having up to 18 non-hydrogen atoms,
and optionally (when R* is not hydrogen), two R* groups from Z, or
an R* group from Z and an R* group from Y form a ring system;
M is titanium, scandium, yttrium or lanthanum in the +3 formal
oxidation state;
L is a divalent derivative of a 2,4-dimethyl-.eta..sup.5
-pentadien-3-yl, cyclohexadienyl, cyclosilahexadienyl, partially
hydrogenated naphthalenyl, partially hydrogenated anthracenyl group
or a hydrocarbyl or silyl substituted derivative of such
cyclohexadienyl, cyclosilahexadienyl, partially hydrogenated
naphthalenyl, partially hydrogenated anthracenyl group, each said
hydrocarbyl or silyl substituent having up to 10 nonhydrogen atoms;
and
X is chloro, allyl or an N,N-dialkylamino substituted hydrocarbyl
group, said X having up to 12 non-hydrogen atoms.
5. A metal complex according to claim 1, corresponding to the
formula: ##STR16## wherein: E is independently each occurrence
silicon or carbon
R" is independently each occurrence hydrogen or C.sub.1-10
hydrocarbyl;
R'" is an aryl, benzyl, hydrocarbyl substituted aryl, hydrocarbyl
substituted benzyl, secondary or tertiary alkyl or tertiary silyl
group of up to 12 nonhydrogen atoms;
M is titanium in the +3 formal oxidation state;
m is an integer from 1 to 3;
L is a (2,4-dimethylpentadien-3-yl), (6,6-disubstituted-.eta..sup.5
-cyclohexadien-3-yl), (6,6-disubstituted-.eta..sup.5
-cyclosilahexadien-3-yl), (1,2,3,4,5-.eta.-cyclohexadien-6-yl),
(6-substituted-1,2,3,4,5-.eta.-cyclohexadien-6-yl),
(1,2,4,5,6,6-hexasubstituted-.eta..sup.5 -cyclohexadien-3-yl)-,
(1,1-disubstituted-.eta..sup.5 -hexahydronaphthalen-4-yl),
(1,1,2,3-tetrasubstituted-.eta..sup.5 -hexahydronaphthalen-4-yl),
or
(9,9-disubstituted-10,11,12,13,14-.eta.-1,2,3,4,5,6,7,8,9,10-decahydroanth
racene-10-yl), group said substituents independently each
occurrence being hydrocarbyl, hydrocarbyloxy, silyl, siloxy or a
mixture thereof of up to 10 nonhydrogen atoms each;
X is chloro or allyl, and X' is THF or MgCl; or X and X' together
is 2-(N,N-dimethylamino)benzyl.
6. A metal complex according to claim 5 selected from the group
consisting of: (tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(Ill)chloride.MgCl;
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanezirconium(Ill)methyl.THF;
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5 -pentadien-1-
yl)silanezirconium)(III)methyl;
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanezirconium(III)(.eta..sup.3 -propenyl);
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanezirconium(III) 2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta..sup
.5 -pentadien-3-yl)silanetitanium(III)chloride.MgCl;
(tert-butylamido)(dimethyl)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta..sup
.5 -pentadien-3-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta..sup
.5
-pentadien-3-yl)silanezirconium(III)chloride.THF;(tert-butylamido)(dimethy
l)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanezirconium(III) 2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)chloride.MgCl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)(.eta..sup.3 -propenyl);
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanezirconium(III)chloride.MgCl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanezirconium(III)
2-(N,N-dimethylamino)benzyl,
(tert-butylamido(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien-3-yl)silanezirconium(III)methyl.THF;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
cyclosilahexadien-3-yl)silanezirconium(III)
2-(N,N-dimethylamino)benzyl,
(N-tert-butylamido)(dimethyl)(2,3,4,9,10-.eta.-1,2-dihydronaphthalen-4-yl)
silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4-dihydronap
hthalen-4-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(1,1
-dimethyl-2,3,4,9,10.eta.-1,2,5,6,7,8-hexahydronaphthalen-4-yl)silanetitan
ium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14-.eta.-9,10-dihyd
roanthracen-10-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14-.eta.-1,2,3,4,9,
10-hexahydroanthracen-10-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10
,11,12,13,14-.eta.-1,2,3,4,5,6,7,8,9,10-decahydroanthracen-10-yl)silanetita
nium(III) 2-(N,N-dimethylamino)benzyl, and
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14-.eta.-1,2,3,4,5,
6,7,8,9,11-decahydroanthracen-10-yl)silanetitanium(III)(.eta..sup.3
-propenyl).
Description
BACKGROUND OF THE INVENTION
This invention relates to certain Group 3,4 and Lanthanide metal
complexes comprising a cyclic, or noncyclic, non-aromatic, anionic,
dienyl group wherein the metal of said complexes is in the +3
formal oxidation state and further wherein the metal is also
covalently bonded via a second ligand group to the cyclic or
noncyclic, non-aromatic, anionic, dienyl ligand group. The
invention also relates to techniques for preparing such complexes,
catalyst systems comprising such complexes that are useful for
polymerizing addition polymerizable monomers, and to such
polymerization processes themselves.
Metal complexes containing delocatized, -bonded ligand groups and
methods for their preparation are disclosed in U.S. application
Ser. No. 545,403, filed Jul. 3, 1990, pending (EP-A-416,815); U.S.
application Ser. No. 547,718, filed Jul. 3, 1990, abandoned
(EP-A-468,651); U.S. application Ser. No. 702,475, filed May 20,
1991, abandoned (EP-A-514,828); U.S. application Ser. No. 876,268,
filed May 1, 1992, pending (EP-A-520,732) and U.S. application Ser.
No. 8,003, filed Jan. 21, 1993, now U.S. Pat. No. 5,374,696
(WO93/19104), as well as U.S. Pat. No. 5,055,438, U.S. Pat. No.
5,057,475, U.S. Pat. No. 5,096,867, U.S. Pat. No. 5,064,802 and
U.S. Pat. No. 5,132,380. The teachings of all the foregoing
patents, publications and patent applications are hereby
incorporated by reference
Despite the advance in the art brought about by the foregoing metal
complexes, new and improved catalytic compounds are still
desired.
SUMMARY OF THE INVENTION
According to the present invention there are provided metal
complexes corresponding to the formula: ##STR1## wherein M is a
Group 3, Group 4 or Lanthanide metal in the +3 formal oxidation
state;
L is a group containing a cyclic or noncyclic, non-aromatic,
anionic, dienyl ligand group bound to M and Z, said L group
containing up to 60 nonhydrogen atoms, and being selected from the
group consisting of 2,4-dimethylpentadienyl-,
1,5-dimethylpentadienyl-, silyl substituted pentadienyl-, silyloxy
substituted pentadienyl-, hydrocarbyloxy substituted pentadienyl-,
cyclohexadienyl-, cyclosilahexadienyl-, cycloheptadienyl-,
cyclooctadienyl-, diphenyl-.eta..sup.5 -methyl-, and
di(1-cyclohexenyl)-.eta..sup.5 -methyl- groups, and inertly
substituted derivatives of such cyclohexadienyl-,
cyclosilahexadienyl-, cycloheptadienyl-, cyclooctadienyl-,
diphenyl-.eta..sup.5 -methyl- and di(1-cyclohexenyl)-.eta..sup.5
-methyl- groups;
Z is a moiety covalently bound to both L and Y, comprising boron,
or a member of Group 14 of the Periodic Table of the Elements, said
moiety having up to 60 non-hydrogen atoms;
Y is a moiety comprising nitrogen, phosphorus, sulfur or oxygen
through which Y is covalently bound to both Z and M, said moiety
having up to 20 nonhydrogen atoms;
X' independently each occurrence is a Lewis base containing up to
40 nonhydrogen atoms;
X is a monovalent anionic moiety having up to 20 non-hydrogen
atoms, provided however that X is not an aromatic group that is
-bonded to M and optionally X and one or more X' groups may be
bonded together thereby forming a moiety that is both covalently
bound to M and coordinated thereto by means of Lewis base
functionality; and
q is a number from 0 to 3.
Additionally according to the present invention there are provided
processes for preparing such complexes comprising contacting a
precursor Group 4 or Lanthanide metal compound containing 2
displaceable ligand groups with a source of a dianionic ligand,
(L-Z-Y).sup.-2, and optionally, if the precursor compound is in a
higher formal oxidation state than the desired product, reducing
the resulting complex.
Further according to the present invention there is provided a
catalyst system useful for polymerization of addition polymerizable
monomers comprising:
A) 1) one or more of the above metal complexes or the reaction
product of the above described process, and 2) one or more
activating cocatalysts;
or
B) the reaction product formed by converting one or more of the
above metal complexes or the reaction product of the above
described process to an active catalyst by use of an activating
technique.
The present invention also provides a polymerization process
comprising contacting one or more addition polymerizable monomers
with a catalyst comprising one or more of the above catalyst
systems. The polymerization may be performed under solution,
suspension, slurry, or gas phase process conditions, and the
composition or individual components thereof may be used in a
heterogeneous, i.e., a supported state, or in a homogeneous state.
The catalyst can be used in combination with one or more additional
catalysts of the same or different nature either simultaneously in
the same or separate reactor or sequentially in the same or
separate reactors.
Catalysts prepared from the complexes of the present invention
possess improved catalytic properties compared to previously known
dienyl based metal complexes. Surprisingly, the present complexes
are stable under a wide variety of operating conditions and
catalyst systems formed therefrom possess desirable operating
features. For example, olefin polymer products formed from catalyst
systems comprising complexes according to the present invention are
relatively low in undesirable internal vinyl unsaturation thereby
making such polymers more resistant to degradation.
DETAILED DESCRIPTION
All reference to the Periodic Table of the Elements herein shall
refer to the Periodic Table of the Elements, published and
copyrighted by CRC Press, Inc., 1989. Also, any reference to a
Group or Groups shall be to the Group or Groups as reflected in
this Periodic Table of the Elements using the IUPAC system for
numbering groups.
Preferably, M is titanium or zirconium, most preferably
titanium.
By the term "non-aromatic" when used with reference to L groups is
meant that the atoms contributing electrons to the -system through
which the anionic ligand is .pi.-bonded to the metal do not form a
cyclic, planar, -system with 4n+2 electrons, where n is an integer
greater than or equal to 0. With respect to the methyldiphenyl
group, i.e.: ##STR2## it should be noted that the group includes
phenyl substituents but the -system through which the ligand is
bound to the metal is an .eta..sup.5 system, not .eta..sup.6.
Examples of aromatic ligand groups which are not included within
the present definition of L include cyclopentadienyl ligands and
substituted cyclopentadienyl ligands (including indenyl, fluorenyl,
and hydrogenated derivatives thereof).
By the term "divalent derivatives" is meant that L is bonded to
both Z and M. Suitable inert substituents on L include hydrogen,
hydrocarbyl, halocarbyl, halohydrocarbyl, silyl, germyl, halo,
amino, phosphino, cyano, hydrocarbyloxy, siloxy and combinations
thereof, each of said inert substituents having up to 20
nonhydrogen atoms, or optionally, two or more such substituents
(except hydrogen, cyano or halo) together form a ring structure,
particularly a fused ring structure. Desirably, such L groups
contain up to 50 non-hydrogen atoms.
Hydrogenated multiple ring ligand groups are specifically included
within the above described L ligands. Dihydronaphthalenyl,
hexahydronaphthalenyl, dihydroanthracenyl, hexahydroanthracenyl,
decahydroanthracenyl groups, and such groups containing one or more
of the foregoing hydrocarbyl, halocarbyl, halohydrocarbyl, silyl,
germyl, halo, amino, phosphino, cyano, hydrocarbyloxy, siloxy
groups or combinations thereof are specifically included within the
above definition of L groups.
Preferred L groups correspond to the following formulas: ##STR3##
wherein: R' in each occurrence is a ligand that is independently
selected from the group consisting of hydrogen, hydrocarbyl, silyl,
germyl, siloxy, amino, hydrocarbyloxy, cyano, halo and combinations
thereof, said R' having up to 20 non-hydrogen atoms, and
optionally, two or more R' groups (where R' is not hydrogen, halo
or cyano) may together form a divalent derivative of one of the
foregoing ligands; and provided further that one R' comprises a
covalent bond to Z.
Especially suitable L groups are selected from the group consisting
of divalent derivatives (as above defined with respect to L) of
2,4-dimethylpentadien-3-yl, cyclohexadienyl, cyclosilahexadienyl,
cycloheptadienyl, or cyclooctadienyl groups; hydrocarbyl, silyl,
hydrocarbyloxy and siloxy substituted derivatives of such groups;
partially hydrogenated anthracenyl, or partially hydrogenated
naphthalenyl groups; and hydrocarbyl, silyl, hydrocarbyloxy or
siloxy substituted derivatives of such partially hydrogenated
anthracenyl or partially hydrogenated naphthalenyl groups.
The dienyl ligand group is bound to the metal atom by any suitable
electronic interaction. In certain circumstances the exact form of
electronic interaction may be indeterminate, because several
equivalent isomeric configurations of the L ligand group may be
generated, i.e., .eta..sup.1 -, .eta..sup.3 -, and .eta..sup.5
-bonded L ligands. This fact has been previously disclosed in the
art, particularly in the teachings of R. D. Ernst, Chem. Rev., 88,
1255-1291 (1988), and R. D. Ernst, et al., J. Am. Chem. Soc. 107,
5016-5018 (1985). Moreover it is further well understood that the
dienyl ligand in an .eta..sup.5 -bonded configuration may be
depicted in several equivalent isomeric configurations, known as
the "W", "U" and "S" configurations. Such isomeric forms are
illustrated with the 2,4-dimethylpentadien-3-yl ligand in the
following drawing: ##STR4## Such variants are not necessarily
separately named herein nor are the carbon atoms contributing to
the dienyl ligand's bonds always identified since the equivalence
of such L groups is well recognized by the skilled artisan, as
illustrated by the above cited Ernst and Ernst, et al. references.
It is to be further understood that in naming the foregoing L
groups, the original positions of the double bonds of the dienyl
ligand need not be identified since in the final delocalized ligand
group the original double bonds no longer exist, i.e., the
.eta..sup.5 -1,3-pentadien-3-yl group is identical to the
.eta..sup.5 -1,4-pentadien-3-yl group. All such isomers are
equivalent and may be referred to simply as .eta..sup.5
-pentadien-3-yl. For purposes of the present invention it is to be
understood that all possible isomeric forms of L are included in
any reference to a specific isomer or electronic structure.
The positional numbering of the L group herein is accomplished by
identifying the carbons contributing to the bonds to M and Z or
where no ambiguity is possible, merely identifying the total
carbons contributing to such bonds with the symbol, .eta.. In
monocyclic systems the lowest ordinals in sequence are assigned to
the carbons contributing to the bonds with the positions otherwise
numbered so as to produce the lowest positional numbers for
substituted carbon atoms. Thus, the trimethyl-substituted
cyclohexadienyl ligand group derived from
1,5,5-trimethyl-1,3-cyclohexadiene and bound at what was the the
2-position (illustrated as follows) ##STR5## is named
(2,6,6-trimethyl-.eta..sup.5 -cyclohexadien-3-yl) rather than
(4,6,6-trimethyl-.eta..sup.5 -cyclohexadien-3-yl) or
(2,2,4-trimethyl-.eta..sup.5 -cyclohexadien-5-yl). The positional
attachment of the Z group is indicated by identifying the carbon
atom followed by -yl, i.e., (.eta..sup.5 -pentadien-1-yl) or
(.eta..sup.5 -pentadien-2-yl). Multicyclic systems are numbered
using standard nomenclature so as to avoid confusion. Specifically,
hydrogenated naphthalenyl and hydrogenated anthracenyl systems are
specifically illustrated as follows: ##STR6## Hydrogenated
positions of multicyclic systems are generally identified herein,
however it is to be further understood that while various isomeric
forms of such hydrogenated ligands are possible they are not
necessarily named herein
Examples of the foregoing L groups include:
(2,4-dimethyl-.eta..sup.5 -pentadien-1-yl),
(2,4-dimethyl-.eta..sup.5 -pentadien-2-yl),
(2,4-dimethyl-.eta..sup.5 -pentadien-3-yl),
(1,5-dimethyl-.eta..sup.5 -pentadien-1-yl),
(1,5-dimethyl-.eta..sup.5 -pentadien-2-yl),
(1,5-dimethyl-.eta..sup.5 -pentadien-3-yl),
(1,5-bis(trimethylsilyl)-.eta..sup.5 -pentadien-3-yl), (.eta..sup.5
-cyclohexadien-1-yl), (.eta..sup.5 -cyclohexadien-2-yl),
(.eta..sup.5 -cyclohexadien-3-yl), (6,6-dimethyl-.eta..sup.5
-cyclohexadien-1-yl), (6,6-dimethyl-.eta..sup.5
-cyclohexadien-2-yl), (6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl), (6,6-dimethyl-.eta..sup.5
-6-sila-cyclohexadien-3-yl), (6-t-butyl-6-methoxy-.eta..sup.5
-6-sila-cyclohexadien-3-yl), (6-methyl-6-fluoro-.eta..sup.5
-6-sila-cyclohexadien-3-yl), (1,2,6,6-tetramethyl-.eta..sup.5
-cyclohexadien-4-yl), (1,2,4,6,6-pentamethyl-.eta..sup.5
-cyclohexadien-3-yl), (1,2,4,6,6-pentamethyl-.eta..sup.5
-cyclohexadien-5-yl), (1,2,5,6,6-pentamethyl-.eta..sup.5
-cyclohexadien-4-yl), (1,2,4,5,6,6-hexamethyl-.eta..sup.5
-cyclohexadien-3-yl),
(1,2,4,5-tetramethyl-6,6-cyclotrimethylene-.eta..sup.5
-cyclohexadien-3-yl),
(2,3,4,9,10-.eta.-1,2-dihydronaphthalen-1-yl), (2,3,4,9,10
-.eta.-1,2-dihydronaphthalen-2-yl),
(1,1-dimethyl-2,3,4,9,10-.eta.-1,2-dihydronaphthalen-2-yl),
(1,1-dimethyl-2,3,4,9,10-.eta.-1,2-dihydronaphthalen-4-yl),
diphenylmethyl, di(1-cyclohexenyl)methyl, the equivalent ligands:
(1,1-dimethyl-2,3,4,9,10-.eta.-1,2,5,6,7,8-hexahydronaphthalen-4-yl),
(1,1-dimethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8-hexahydronaphthalen-4-yl),
and
(1,1-dimethyl-2,3,4,9,10-.eta.-1,5,6,7,8,9-hexahydronaphthalen-4-yl),
the equivalent ligands (1,1,2,
3-tetramethyl-2,3,4,9,10-.eta.-1,2,5,6,7,8-hexahydronaphthalen-4-yl),
(1,1,2,3-tetramethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8-hexahydronaphthalen-4-yl
), and
(1,1,2,3-tetramethyl-2,3,4,9,10-.eta.-1,5,6,7,8,9-hexahydronaphthalen-4-yl
), (10,11,12,13,14-.eta.-9,10-dihydroanthracen-9-yl),
(10,11,12,13,14-.eta.-9,10-dihydroanthracen-1-yl),
(9,9-dimethyl-10,11,12,13,14-.eta.-9,10-dihydroanthracen-10-yl),
(10,11,12,13,14-.eta.-1,2,3,4,9,10-hexahydroanthracen-9-yl),
(10,11,12,13,14-.eta.-1,2,3,4, 9,10-hexahydroanthracen-1 -yl),
(10,11,12,13,14-.eta.-1,2,3,4, 9,11-hexahydroanthracen-9-yl),
(10,11,12,13,14-.eta.-1,4,5,8,9,10-hexahydroanthracen-1-yl),
(9,9-dimethyl-10,11,12,13,14-.eta.-1,4,5,8,9,10-hexahydroanthracen-10-yl),
(9,9-dimethyl-10,11,12,13,14-.eta.-1,4,5,8,9,10-hexahydroanthracen-2-yl),
(8,8-dimethyl-5,6,7,13,14-.eta.-1,4,5,8,9,1
0-hexahydroanthracen-10-yl), the equivalent ligands:
(10,11,12,13,14-.eta.-1,2,3,4,5,6,7,8,9,10-decahydroanthracen-
9-yl) and
(10,11,12,13,14-.eta.-1,2,3,4,5,6,7,8,9,11-decahydroanthracen-9-yl);
and the equivalent ligands:
(9,9-dimethyl-10,11,12,13,14-.eta.-1,2,3,4,5,6,7,8,9,10-decahydroanthracen
-10-yl) and
(9,9-dimethyl-10,11,12,13,14-.eta.-1,2,3,4,5,6,7,8,9,11-decahydroanthracen
-10-yl)
These groups are further illustrated in the following structures:
##STR7##
Examples of X include chloro, hydrocarbyl, hydrocarbyloxy said X
having up to 12 non-hydrogen atoms. Preferred examples of X groups
are halide groups, allyl and methyl-substituted allyl stabilizing
ligands. Preferred examples of X and X' groups taken together are
di(hydrocarbyl)amino-, hydrocarbyloxy-, and
di(hydrocarbyl)phosphino-substituted hydrocarbyl or silyl groups of
up to 20 nonhydrogen atoms. Most preferred X groups are allyl. Most
preferred X and X' groups taken together are dialkylaminobenzyl
groups having from 1 to 4 carbons in each alkyl group.
Preferred X' groups (when not bonded to X) include phosphines,
phosphites, ethers, amines, carbon monoxide, salts of Group 1 or 2
metals, and mixtures of the foregoing X' groups. Examples of the
foregoing especially include trimethylphosphine, triethylphosphine,
trifluorophosphine, triphenylphosphine,
bis-1,2-(dimethylphosphino)ethane, trimethylphosphite,
triethylphosphite, dimethylphenylphosphite, tetrahydrofuran,
diethyl ether, carbon monoxide, pyridine, bipyridine,
tetramethylethylenediamine (TMEDA), dimethoxyethane (DME), dioxane,
triethylamine, lithium chloride, and magnesium chloride.
Preferred metal coordination complexes according to the present
invention correspond to the formula: ##STR8## wherein: Y is --O--,
--S--, --NR*--, --PR*--;
Z is SiR*.sub.2, CR*.sub.2, SiR*.sub.2 SiR*.sub.2, CR*.sub.2
CR*.sub.2, CR*.dbd.CR*, CR*.sub.2 SiR*.sub.2, CR*.sub.2 CR*.sub.2
CR*.sub.2, CR*.sub.2 SiR*.sub.2 CR*.sub.2, SiR*.sub.2 CR*.sub.2
CR*.sub.2, SiR*.sub.2 CR*.sub.2 SiR*.sub.2, SiR*.sub.2 SiR*.sub.2
CR*.sub.2, SiR*.sub.2 SiR*.sub.2 SiR*.sub.2, or GeR*.sub.2;
wherein:
R* each occurrence is independently hydrogen, or a member selected
from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and
combinations thereof, said R* having up to 18 non-hydrogen atoms,
and optionally (when R* is not hydrogen), two R* groups from Z, or
an R* group from Z and an R* group from Y form a ring system.
M is titanium, scandium, yttrium or lanthanium in the +3 formal
oxidation state;
L is a divalent derivative of a 2,4-dimethyl-.eta..sup.5
-pentadien-3-yl, cyclohexadienyl, cyclosilahexadienyl, partially
hydrogenated naphthalenyl, partially hydrogenated anthracenyl group
or a hydrocarbyl or silyl substituted derivative of such
cyclohexadienyl, cyclosilahexadienyl, partially hydrogenated
naphthalenyl, partially hydrogenated anthracenyl group, each said
hydrocarbyl or silyl substituent having up to 10 nonhydrogen atoms;
and
X is chloro, allyl or an N, N-dialkylamino substituted hydrocarbyl
group, said X having up to 12 non-hydrogen atoms.
Most highly preferred metal coordination complexes are amidosilane-
or amidoalkanediyl- compounds corresponding to the formula:
##STR9## wherein: E is independently each occurrence silicon or
carbon.
R" is independently each occurrence hydrogen or C.sub.1-10
hydrocarbyl;
R'" is an aryl, benzyl, hydrocarbyl substituted aryl, hydrocarbyl
substituted benzyl, secondary or tertiary alkyl or tertiary silyl
group of up to 12 nonhydrogen atoms;
M is titanium in the +3 formal oxidation state;
m is an integer from 1 to 3;
L is a (2,4-dimethylpentadien-3-yl), (6,6-disubstituted-.eta..sup.5
-cyclohexadien-3-yl), (6,6-disubstituted-.eta..sup.5
-cyclosilahexadien-3-yl), (1,2,3,4,5-.eta.-cyclohexadien-6-yl),
(6-substituted-1,2,3,4,5-.eta.-cyclohexadien-6-yl),
1,2,4,5,6,6-hexasubstituted-.eta..sup.5 -cyclohexadien-3-yl)-,
(1,1-disubstituted-.eta..sup.5 -hexahydronaphthalen-4-yl),
(1,1,2,3-tetrasubstituted-.eta..sup.5 -hexahydronaphthalen-4-yl),
or
(9,9-disubstituted-10,11,12,13,14-.eta.-1,2,3,4,5,6,7,8,9,10-decahydroanth
racene-10-yl), group said substituents independently each
occurrence being hydrocarbyl, hydrocarbyloxy, silyl, siloxy or a
mixture thereof of up to 10 nonhydrogen atoms each;
X is chloro or allyl, and X' is THF or MgCl; or X and X' together
is 2-(N,N-dimethylamino)benzyl.
As a means of further illustration of the invention, specific metal
complexes included therein are:
Substituted pentadienyl complexes
(N-tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-1-yl)silanetitanium(III)chloride.MgCl;
(N-tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III)methyl.THF;
(N-tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III)bis(trimethylsilyl)methyl;
(N-tert-butylamido)(diphenyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-benzylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III) (.eta..sup.3 -propenyl);
(N-tert-butylamido)(tetramethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)disilanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(tetramethyl)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta
..sup.5 -pentadien-1-yl)disilanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(1,1,2,2-tetramethyl)(1,5-bis(trimethylsilyl)-2,4-dimet
hyl-.eta..sup.5 -pentadien-3-yl)disilanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(1,1,2,2-tetramethyl)(.eta..sup.5
-2,4-dimethylpentadien-3-yl)disilanetitanium(III)(.eta..sup.3
-propenyl);
(N-tert-butylamidomethylene)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-ylmethylene)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-1-yl)silanetitanium(III)(.eta..sup.3 -propenyl);
(N-tert-butylamido)(dimethyl)(1,5-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III) chloride.MgCl;
(N-phenylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-1yl)silanetitanium(III) (.eta..sup.3 -propenyl);
(N-cyclododecyl)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III)methyl.THF;
(N-tert-butylamido)(dimethyl)(1,5-bis(trimethylsilylmethyl)-.eta..sup.5
-pentadien-3-yl)silanetitanium(III) methyl, THF;
1-(N-tert-butylamido)-2-(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)ethane-l,2-diyltitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(1,5-di(trimethylsilyl)
2,4-dimethyl-r[5-pentadien- 3yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl; and
(N-tert-butylamido)(dimethyl)(1,5-bis(trimethylsilyl)-.eta..sup.5
-pentadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl.
Cyclohexadienyl and substituted cyclohexadienyl complexes
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-cyclohexadien-1-yl)silanetitanium(III)chloride.MgCl;
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-cyclohexadien-1-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-1-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(diphenyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(1,1,2,2-tetramethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-1-yl)disilanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(1,1,2,2-tetramethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)disilanetitanium(III)
2-(N,N-dimethylamino)benzyl;
((N-tert-butylamido)methyl)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)((6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)methyl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(2,4-dimethoxy-6
,6-dimethyl-.eta..sup.5 -cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-benzylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(1,2,4,5,6,6-hexamethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl; (N-tert-butylamido)(dimethyl)(1,2,
6,6-tetramethyl-.eta..sup.5 -cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)methyl.THF;
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-cyclohexadien-1-yl)silanetitanium(IV)(.eta..sup.3 -propenyl);
(N-tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)chloride.MgCl;
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-cyclohexadien-1-yl)silanetitanium(III)(.eta..sup.3 -propenyl);
(N-tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)chloride.MgCl;
(N-dodecyl)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)chloride.MgCl;
(N-tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)trimethylsilylmethyl;
(N-tert-amylamido)(dimethyl)(6 t-butyl-6-methoxy-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
1-(N-tert-butylamido)-2-(6,6-dimethyl-.eta..sup.5 -cyclohexadien-
3-yl)ethanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(2,3,4,9,10-.eta.-1,2-dihydronaphthalen-1-yl)
silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4-dihydronap
hthalen-4-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(2,3,4,9,10-.eta.-1,2,
5,6,7,8-hexahydronaphthalen-1-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(1,1-dimethyl-2,3,4,9,10-.eta.-1,2,5,6,7,8-he
xahydronaphthalen-4-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl)-10,11,12,13,14-.eta.-9,10-dihy
droanthracen-10-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14-.eta.-1,2,3,4,
9,10-hexahydroanthracen-10-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14-.eta.-1,2,3,4,5,
6,7,8,9,10-decahydroanthracen-10-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl, and
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14.eta.-1,2,3,4,5,6
,7,8,9,11-decahydroanthracen-10-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl.
Higher cycloalkadienyl and other complexes
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-cycloheptadien-1-yl)silanetitanium(III)chloride.MgCl;
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-cyclooctadien-1-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-cyclooctadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(6,6,7,7-tetramethyl-.eta..sup.5
-cycloheptadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(6,7,8-trimethyl-.eta..sup.5
-cyclooctadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(1,1,2,2-tetramethyl)(6,6-dimethyl-.eta..sup.5
-cycloheptadien-3-yl)disilanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(1,1,2,2-tetramethyl)(6,7,8-trimethyl-.eta..sup.5
-cyclooctadien-3-yl)disilanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-di(1-cyclohexenyl)methyl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamidomethyl)(dimethyl)(.eta..sup.5
-diphenylmethyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-diphenylmethyl)silanetitanium(III)chloride.MgCl;
(N-tert-butylamido)(dimethyl)(.eta..sup.5
-diphenylmethyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(6-t-butyl-6-methoxy-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(6-methyl-6-methoxy-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl; and
(N-tert-butylamido)(dimethyl)(6,7,7,8-tetramethyl-.eta..sup.5
-cyclooctadien- 3-yl)silanetitanium(III)(.eta..sup.3
-propenyl).
The skilled artisan will recognize that additional members of the
foregoing list include the corresponding Group 3 and Lanthanide
containing derivatives, as well as complexes that are substituted
as herein defined.
Most highly preferred metal complexes according to the present
invention comprise:
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III)chloride.MgCl;
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanezirconium(III)methyl.THF;
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-1-yl)silanezirconium(III)methyl;
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanezirconium(III)(.eta..sup.3 -propenyl);
(tert-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-3-yl)silanezirconium(III) 2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta..sup
.5 -pentadien-3-yl)silanetitanium(III)chloride.MgCl;
(tert-butylamido)(dimethyl)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta..sup
.5 -pentadien-3-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta..sup
.5 -pentadien-3-yl)silanezirconium(III)chloride.THF;
(tert-butylamido)(dimethyl)(1,5-bis(trimethylsilyl)-2,4-dimethyl-.eta..sup
.5 -pentadien-3-yl)silanezirconium(III)
2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)chloride.MgCl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)(.eta..sup.3 -propenyl);
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien-3-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanezirconium(III)chloride.MgCl;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanezirconium(III)
2-(N,N-dimethylamino)benzyl,
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien- 3-yl)silanezirconium(III)methyl.THF;
(tert-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclosilahexadien-3-yl)silanezirconium(III)
2-(N,N-dimethylamino)benzyl,
(N-tert-butylamido)(dimethyl)(2,3,4,9,10-.eta.-1,2-dihydronaphthalen-4-yl)
silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4-dihydronap
hthalen-4-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(2,3,4,9,10-.eta.-1,2,5,6,7,8-hexahydronaphth
alen-4-yl)silanetitanium(III) (trimethylsilyl)methyl;
(N-tert-butylamido)(dimethyl)(1,1-dimethyl-2,3,4,9,10-.eta.-1,2,5,6,7,8-he
xahydronaphthalen-4-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14-.eta.-9,10-dihyd
roanthracen-10-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14-.eta.-1,2,3,4,9,
10-hexahydroanthracen-10-yl)silanetitanium(III)
2-(N,N-dimethylamino)benzyl;
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10
,11,12,13,14-.eta.-1,2,3,4,5,6,7,8,9,10-decahydroanthracen-10-yl)silanetita
nium(III) 2-(N,N-dimethylamino)benzyl, and
(N-tert-butylamido)(dimethyl)(9,9-dimethyl-10,11,12,13,14-.eta.-1,2,3,4,5,
6,7,8,9,11-decahydroanthracen-10-yl)silanetitanium(III)(.eta..sup.3
-propenyl).
The complexes can be prepared in one embodiment by combining a
precursor metal compound corresponding to the formula M(X).sub.3
X'.sub.q, wherein M, s X, X' and q are as previously defined, with
the added proviso that X in two occurrences is a monovalent anionic
moiety having up to 20 non-hydrogen atoms capable of displacement
by a dianion ligand, (L-Z-Y).sup.-2, wherein L, Z, and Y are as
previously defined, with a metallated derivative of the dianion
ligand (Z-L-Y).sup.-2, with a silyl-, especially a trialkylsilyl-,
derivative of the dianion ligand (Z-L-Y).sup.-2, said silyl- or
trialkylsilyl- group having from 1 to 20 nonhydrogen atoms, or with
the neutral compound, H-(Z-L-Y)-H. The reaction may optionally be
performed in the presence of a Lewis base, X'. The reaction is
preferably conducted in an inert, organic, liquid at a temperature
from -100.degree. to 300.degree. C., preferably from -78.degree. to
150.degree. C., most preferably from 0 to 125.degree. C. The
complex is optionally recovered from the reaction mixture. Suitable
metallated derivatives especially include lithium, sodium,
potassium, magnesium, or Grignard derivatives of the dianion
ligand. Suitable trialkylsilyl derivatives especially include
trimethylsilyl derivatives of the dianion ligand.
The complexes can also be prepared by combining, in the presence o
of a reducing agent, a precursor metal compound corresponding to
the formula M(X).sub.4 X'.sub.q, wherein M, X, X' and q are as
previously defined, with the added proviso that X in two
occurrences is a monovalent anionic moiety having up to 20
non-hydrogen atoms capable of displacement by a dianion ligand,
(L-Z-Y).sup.-2, wherein L, Z, and Y are as previously defined, with
a metatlated derivative of the dianion ligand (Z-L-Y).sup.-2, with
a silyl-, especially a trialkylsilyl-, derivative of the dianion
ligand (Z-L-Y).sup.-2, said silyl- or trialkylsilyl- group having
from 1 to 20 nonhydrogen atoms, or with the neutral compound,
H-(Z-L-Y)-H. The reaction may optionally also be performed in the
presence of a Lewis base, X'. The reaction is preferably conducted
in an inert, organic, liquid at a temperature from -100.degree. to
300.degree. C., preferably from -78.degree. to 150.degree. C., most
preferably from 0.degree. to 125.degree. C. The complex is
optionally recovered from the reaction mixture. Suitable metallated
derivatives especially include lithium, sodium, potassium,
magnesium, or Grignard derivatives of the dianion ligand. Suitable
trialkylsilyl derivatives especially include trimethylsilyl
derivatives of the dianion ligand. Suitable reducing agents
especially include n-butyl lithium, lithium or magnesium metal.
The dianionic ligand group is prepared using standard synthetic
measures known to the skilled artisan or by use of procedures
analogous to previously known routes. The ligands containing
cyclosilahexadienyl functionality are prepared in a manner
analogous to the techniques disclosed in Jutzi, et al, Chem. Ber.,
117, 1885-95 (1984); J. Am. Chem. Soc., 103 6788-6789 (1981); and
Zh. Oshch. Khim., 44, 226-227 (1979), modified according to
EP-A-563,365 as to the particular silane ligand utilized.
Suitable reaction media for the formation of the complexes are
aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers.
Examples include straight and branched-chain hydrocarbons such as
isobutane, butane, pentane, hexane, heptane, octane, and mixtures
thereof; cyclic and alicyclic hydrocarbons such as cyclohexane,
cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures
thereof; aromatic and hydrocarbyl-substituted aromatic compounds
such as benzene, toluene, xylene, and styrene, alkyl ethers having
from 1 to 4 carbons in each alkyl group; C.sub.1-4 dialkyl ether
derivatives of (poly)alkylene glycols, and tetrahydrofuran.
Mixtures of the foregoing are also suitable. Preferred solvents
include C.sub.5-10 alkanes, dialkyl ethers having from 1 to 4
carbons in each alkyl group, tetrahydrofuran, toluene, and mixtures
thereof. Solvated adducts of the metal precursor complex may also
be used if desired. Examples of solvated adducts include pyridine-,
diethylether-, tetrahydrofuran-(THF), 1,2-dimethoxyethane-(DME), or
tetramethyl-ethylenediamine-(TMEDA) containing adducts.
The complexes according to the present invention are surprisingly
stable and readily synthesized. They are active addition
polymerization catalysts alone or when combined with an activating
cocatalyst or used with an activating technique. Suitable
activating cocatalysts for use herein include polymeric or
oligomeric alumoxanes, especially methylalumoxane, triisobutyl
aluminum modified methylalumoxane, or isobutylalumoxane; neutral
Lewis acids, such as C.sub.1-30 hydrocarbyl substituted Group 13
compounds, especially tri(hydrocarbyl)aluminum- or
tri(hydrocarbyl)boron compounds and halogenated (including
perhalogenated) derivatives thereof, having from 1 to 10 carbons in
each hydrocarbyl or halogenated hydrocarbyl group, more especially
perfluorinated tri(aryl)boron compounds, and most especially
tris(pentafluorophenyl)borane; nonpolymeric, compatible,
noncoordinating, ion forming compounds (including the use of such
compounds under oxidizing conditions), especially the use of
ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or
sulfonium- salts of compatible, noncoordinating anions, or
ferrocenium salts of compatible, noncoordinating anions; bulk
electrolysis (explained in more detail hereinafter); and
combinations of the foregoing activating cocatalysts and
techniques. The foregoing activating cocatalysts and activating
techniques have been previously taught with respect to different
metal complexes in the following references: EP-A-277,003, U.S.
Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, EP-A-468,651
(equivalent to U.S. Ser. No. 07/547,718), EP-A-520,732 (equivalent
to U.S. Ser. No. 07/876,268), and EP-A-520,732 (equivalent to U.S.
Ser. Nos. 07/884,966 filed May 1,1992 now U.S. Pat. No. 5,350,723),
the teachings of which are hereby incorporated by reference.
Combinations of neutral Lewis acids, especially the combination of
a trialkyl aluminum compound having from 1 to 4 carbons in each
alkyl group and a halogenated tri(hydrocarbyl)boron compound having
from 1 to 10 carbons in each hydrocarbyl group, especially
tris(pentafluorophenyl)borane, further combinations of such neutral
Lewis acid mixtures with a polymeric or oligomeric alumoxane, and
combinations of a single neutral Lewis acid, especially
tris(pentafluorophenyl)borane with a polymeric or oligomeric
alumoxane are especially desirable activating cocatalysts.
Suitable ion forming compounds useful as cocatalysts in one
embodiment of the present invention comprise a cation which is a
Bronsted acid capable of donating a proton, and a compatible,
noncoordinating anion, A.sup.-. As used herein, the term
"noncoordinating" means an anion or substance which either does not
coordinate to the Group 4 metal containing precursor complex and
the catalytic derivative derived therefrom, or which is only weakly
coordinated to such complexes thereby remaining sufficiently labile
to be displaced by a neutral Lewis base. A noncoordinating anion
specifically refers to an anion which when functioning as a charge
balancing anion in a cationic metal complex does not transfer an an
ionic substituent or fragment thereof to said cation thereby
forming neutral complexes. "Compatible anions" are anions which are
not degraded to neutrality when the initially formed complex
decomposes and are noninterfering with desired subsequent
polymerization or other uses of the complex.
Preferred anions are those containing a single coordination complex
comprising a charge-bearing metal or metalloid core which anion is
capable of balancing the charge of the active catalyst species (the
metal cation) which may be formed when the two components are
combined. Also, said anion should be sufficiently labile to be
displaced by olefinic, diolefinic and acetylenically unsaturated
compounds or other neutral Lewis bases such as ethers or nitriles.
Suitable metals include, but are not limited to, aluminum, gold and
platinum. Suitable metalloids include, but are not limited to,
boron, phosphorus, and silicon. Compounds containing anions which
comprise coordination complexes containing a single metal or
metalloid atom are, of course, well known and many, particularly
such compounds containing a single boron atom in the anion portion,
are available commercially.
Preferably such cocatalysts may be represented by the following
general formula:ps
wherein:
L* is a neutral Lewis base;
(L*-H).sup.+ is a Bronsted acid;
A.sup.d- is a noncoordinating, compatible anion having a charge of
d-, and
d is an integer from 1 to 3.
More preferably A.sup.d- corresponds to the formula: [M.sup.'k+
Q.sub.n' ].sup.d- wherein:
k is an integer from 1 to 3;
n' is an integer from 2 to 6;
n.sup.40 -k=d;
M' is an element selected from Group 13 of the Periodic Table of
the Elements; and
Q independently each occurrence is selected from hydride,
dialkylamido, halide, hydrocarbyl, hydrocarbyloxide,
halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and
halo- substituted silyl-hydrocarbyl radicals (including
perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and
perhalogenated silylhydrocarbyl radicals), said Q having up to 20
carbons with the proviso that in not more than one occurrence is Q
halide. Examples of suitable hydrocarbyloxide Q groups are
disclosed in U.S. Pat. No. 5,296,433, the teachings of which are
herein incorporated by reference.
In a more preferred embodiment, d is one, i.e., the counter ion has
a single negative charge and is A.sup.-. Activating cocatalysts
comprising boron which are particularly useful in the preparation
of catalysts of this invention may be represented by the following
general formula: [L*-H].sup.+ [BQ.sub.4 ].sup.- wherein:
L* is as previously defined;
B is boron in a valence state of 3; and
Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,
fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group
of up to 20 nonhydrogen atoms, with the proviso that in not more
than one occasion is Q hydrocarbyl.
Most preferably, Q is each occurrence a fluorinated aryl group,
especially, a pentafluorophenyl group.
Illustrative, but not limiting, examples of boron compounds which
may be used as an activating cocatalyst in the preparation of the
improved catalysts of this invention are tri-substituted ammonium
salts such as:
trimethylammonium tetraphenylborate,
triethylammonium tetraphenylborate,
tripropylammonium tetraphenylborate,
tri(n-butyl)ammonium tetraphenylborate,
tri(t-butyl)ammonium tetraphenylborate,
N,N-dimethylanilinium tetraphenylborate,
N,N-diethylanilinium tetraphenylborate,
N,N-dimethyl-2,4,6-trimethylanilinium tetraphenylborate,
trimethylammonium tetrakis(pentafluorophenyl)borate,
triethylammonium tetrakis(pentafluorophenyl)borate,
tripropylammonium tetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,
tri(secbutyl)ammonium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate,
N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,
5,6-tetrafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3,
5,6-tetrafluorophenyl)borate,
N,N-dimethylanilinium
pentafluorolphenoxytris(pentafluorophenyl)borate,
N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-dimethyl-2,4,6-trimethylanilinium
tetrakis(pentafluorophenyl)borate,
trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,
triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,
tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,
dimethyl(t-butyl)ammonium
tetrakis(2,3,4,6-tetrafluorophenyl)borate,
N,N-dimethylanilinium
tetrakis(2,3,4,6-tetrafluorophenyl)borate,
N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,
and
N,N-dimethyl-2,4,6-trimethylanilinium
tetrakis(2,3,4,6-tetrafluorophenyl)borate;
dialkyl ammonium salts such as:
di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, and
dicyclohexylammonium tetrakis(pentafluorophenyl)borate;
tri-substituted phosphonium salts such as:
triphenylphosphonium tetrakis(pentafluorophenyl)borate,
tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, and
tri(2,6-dimethylphenyl)phosphonium
tetrakis(pentafluorophenyl)borate;
di-substituted oxonium salts such as:
diphenyloxonium tetrakis(pentafluorophenyl)borate,
di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and
di(2,6-dimethylphenyl)oxonium
tetrakis(pentafluorophenyl)borate;
di-substituted sulfonium salts such as:
diphenylsulfonium tetrakis(pentafluorophenyl)borate,
di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and
di(2,6-dimethylphenyl)sulfonium
tetrakis(pentafluorophenyl)borate.
Preferred [L*-H].sup.+ cations are N,N-dimethylanilinium and
tributylammonium.
Another suitable ion forming, activating cocatalyst comprises a
salt of a cationic oxidizing agent and a noncoordinating,
compatible anion represented by the formula:
wherein:
Ox.sup.e + is a cationic oxidizing agent having a charge of e
+;
e is an integer from 1 to 3; and
A.sup.d- and d are as previously defined.
Examples of cationic oxidizing agents include: ferrocenium,
hydrocarbyl-substituted ferrocenium, Ag .sup.+, or Pb .sup.+2.
Preferred embodiments of A.sup.d- are those anions previously
defined with respect to the Bronsted acid containing activating
cocatalysts, especially tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a
compound which is a salt of a carbenium ion and a noncoordinating,
compatible anion represented by the formula:
wherein:
c.sup.+ is a C.sub.1-20 carbenium ion; and
A.sup.- is as previously defined. A preferred carbenium ion is the
trityl cation, i.e. triphenylmethylium.
A further suitable ion forming, activating cocatalyst comprises a
compound which is a salt of a silylium ion and a noncoordinating,
compatible anion represented by the formula:
wherein:
R is C.sub.1-10 hydrocarbyl, and X', q and A.sup.- are as
previously defined.
Preferred silylium salt activating cocatalysts are
trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium
tetrakispentafluorophenylborate and ether substituted adducts
thereof. Silylium salts have been previously generically disclosed
in J. Chem Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J.
B., et al., Organometallics, 1994, 13, 2430-2443. The use of the
above silylium salts as activating cocatalysts for addition
polymerization catalysts is claimed in U.S. patent application Ser.
No. 08/304,314, pending, entitled, Silylium Cationic Polymerization
Activators For Metallocene Complexes, filed in the names of David
Neithamer, David Devore, Robert LaPointe and Robert Mussell on even
date herewith.
Certain complexes of alcohols, mercaptans, silanols, and oximes
with tris(pentafluorophenyl)borane are also effective catalyst
activators and may be used according to the present invention. Such
cocatalysts are disclosed in U.S. Pat. No. 5,296,433, the teachings
of which are herein incorporated by reference.
The technique of bulk electrolysis involves the electrochemical
oxidation of the metal complex under electrolysis conditions in the
presence of a supporting electrolyte comprising a noncoordinating,
inert anion. In the technique, solvents, supporting electrolytes
and electrolytic potentials for the electrolysis are used such that
electrolysis byproducts that would render the metal complex
catalytically inactive are not substantially formed during the
reaction. More particularly, suitable solvents are materials that
are: liquids under the conditions of the electrolysis (generally
temperatures from 0.degree. to 100.degree. C.), capable of
dissolving the supporting electrolyte, and inert. "Inert solvents"
are those that are not reduced or oxidized under the reaction
conditions employed for the electrolysis. It is generally possible
in view of the desired electrolysis reaction to choose a solvent
and a supporting electrolyte that are unaffected by the electrical
potential used for the desired electrolysis. Preferred solvents
include difluorobenzene (all isomers), dimethoxyethane (DME), and
mixtures thereof.
The electrolysis may be conducted in a standard electrolytic cell
containing an anode and cathode (also referred to as the working
electrode and counter electrode respectively). Suitable materials
of construction for the cell are glass, plastic, ceramic and glass
coated metal. The electrodes are prepared from inert conductive
materials, by which are meant conductive materials that are
unaffected by the reaction mixture or reaction conditions. Platinum
or palladium are preferred inert conductive materials. Normally an
ion permeable membrane such as a fine glass frit separates the cell
into separate compartments, the working electrode compartment and
counter electrode compartment. The working electrode is immersed in
a reaction medium comprising the metal complex to be activated,
solvent, supporting is electrolyte, and any other materials desired
for moderating the electrolysis or stabilizing the resulting
complex. The counter electrode is immersed in a mixture of the
solvent and supporting electrolyte. The desired voltage may be
determined by theoretical calculations or experimentally by
sweeping the cell using a reference electrode such as a silver
electrode immersed in the cell electrolyte. The background cell
current, the current draw in the absence of the desired
electrolysis, is also determined. The electrolysis is completed
when the current drops from the desired level to the background
level. In this manner, complete conversion of the initial metal
complex can be easily detected.
Suitable supporting electrolytes are salts comprising a cation and
a compatible, noncoordinating anion, A.sup.-. Preferred supporting
electrolytes are salts corresponding to the formula G.sup.+ A.sup.-
; wherein:
G.sup.+ is a cation which is nonreactive towards the starting and
resulting complex, and
A.sup.- is as previously defined.
Examples of cations, G.sup.+, include tetrahydrocarbyl substituted
ammonium or phosphonium cations having up to 40 nonhydrogen atoms.
Preferred cations are the tetra-n-butylammonium- and
tetraethylammoniumcations.
During activation of the complexes of the present invention by bulk
electrolysis the cation of the supporting electrolyte passes to the
counter electrode and A.sup.- migrates to the working electrode to
become the anion of the resulting oxidized product. Either the
solvent or the cation of the supporting electrolyte is reduced at
the counter electrode in equal molar quantity with the amount of
oxidized metal complex formed at the working electrode. Preferred
supporting electrolytes are tetrahydrocarbylammonium salts of
tetrakis(perfluoroaryl)borates having from 1 to 10 carbons in each
hydrocarbyl or perfluoroaryl group, especially
tetra-n-butylammonium tetrakis(pentafluorophenyl)borate.
A further recently discovered electrochemical technique for
generation of activating cocatalysts is the electrolysis of a
disilane compound in the presence of a source of a noncoordinating
compatible anion. This technique is more fully disclosed and
claimed in the previously mentioned United States Patent
application entitled, "Silylium Cationic Polymerization Activators
For Metallocene Complexes", filed on even date herewith.
The foregoing activating techniques and ion forming cocatalysts are
also preferably used in combination with a tri(hydrocarbyl)aluminum
or tri(hydrocarbyl)borane compound having from 1 to 4 carbons in
each hydrocarbyl group, an oligomeric or polymeric alumoxane
compound, or a mixture of a tri(hydrocarbyl)aluminum compound
having from 1 to 4 carbons in each hydrocarbyl group and a
polymeric or oligomeric alumoxane.
The molar ratio of catalyst/cocatalyst employed preferably ranges
from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most
preferably from 1:10 to 1:1. In a particularly preferred embodiment
of the invention the cocatalyst can be used in combination with a
tri(hydrocarbyl)aluminum compound having from 1 to 10 carbons in
each hydrocarbyl group or an oligomeric or polymeric alumoxane.
Mixtures of activating cocatalysts may also be employed. It is
possible to employ these aluminum compounds for their beneficial
ability to scavenge impurities such as oxygen, water, and aldehydes
from the polymerization mixture. Preferred aluminum compounds
include trialkyl aluminum compounds having from 2 to 6 carbons in
each alkyl group, especially those wherein the alkyl groups are
methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl,
neopentyl, or isopentyl, and methylalumoxane, modified
methylalumoxane (that is, methylalumoxane modified by reaction with
triisobutyl aluminum) (MMAO) and isobutylalumoxane. The molar ratio
of metal complex to aluminum compound is preferably from 1:10,000
to 100:1, more preferably from 1:1000 to 10:1, most preferably from
1:500 to 1:1. A most preferred activating cocatalyst comprises both
a strong Lewis acid and an alumoxane, especially
tris(pentafluorophenyl)borane and methylalumoxane, modified
methylalumoxane, or diisobutylalumoxane.
The catalysts may be used to polymerize ethylenically and/or
acetylenically unsaturated monomers having from 2 to 100,000 carbon
atoms either alone or in combination. Preferred monomers include
the C.sub.2-20 .alpha.-olefins especially ethylene, propylene,
isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene,
4-methyl-1-pentene, 1-octene, 1-decene, long chain, macromolecular
.alpha.-olefins, and mixtures thereof. Other preferred monomers
include styrene, C.sub.1-4 alkyl substituted styrene,
tetrafluoroethylene, vinylbenzocyclobutane, ethylidenenorbornene,
1,4-hexadiene, 1, 5-hexadiene, 1,7-octadiene, vinylcyclohexane,
4-vinylcyclohexene, allylbenzene, divinylbenzene,
2,5-norbornadiene, and mixtures of such other preferred monomers
with C.sub.2-20 .alpha.-olefins.
In general, the polymerization may be accomplished at conditions
well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type
polymerization reactions, i.e., temperatures from
0.degree.-250.degree. C. and pressures from atmospheric to 10,000
atmospheres (0.1 to 1000 MPa). Suspension, solution, slurry, gas
phase or other process conditions may be employed if desired. A
support, especially silica, modified silica (silica modified by
calcining, treatment with a trialkylaluminum compound having from 1
to 10 carbons in each alkyl group, or treatment with an
alkylalumoxane), alumina, or a polymer (especially
polytetrafluoroethylene or a polyolefin) may be employed, and
desirably is employed when the catalysts are used in a gas phase or
slurry polymerization process. The support is preferably employed
in an amount to provide a weight ratio of catalyst (based on
metal):support from 1:100,000 to 1:10, more preferably from
1:50,000 to 1:20, and most preferably from 1:10,000 to 1:30.
In most polymerization reactions the molar ratio of
catalyst:polymerizable compounds employed is from 10.sup.-12 :1 to
10.sup.-1 :1, more preferably from 10.sup.-12 :1 to 10.sup.-5
:1.
Suitable solvents or diluents for polymerization are
noncoordinating, inert liquids. Examples include C.sub.4-10
straight and branched-chain hydrocarbons, especially butane,
isobutane, pentane, isopentane, hexane, heptane, octane, and
mixtures thereof; cyclic and alicyclic hydrocarbons such as
cyclopentane, cyclohexane, cycloheptane, methylcyclohexane,
methylcycloheptane, and mixtures thereof; perfluorinated
hydrocarbons such as perfluorinated C.sub.4-10 alkanes, and
aromatic and alkyl-substituted aromatic compounds such as benzene,
toluene, and xylene (all isomers). Suitable solvents also include
liquid olefins or other monomers or mixtures thereof as previously
mentioned.
The catalysts may also be utilized in combination with at least one
additional homogeneous or heterogeneous polymerization catalyst in
the same or separate reactors connected in series or in parallel to
prepare polymer blends having desirable properties. An example of
such a process is disclosed in WO 94/00500, equivalent to U.S. Ser.
No. 07/904,770, abandoned as well as U.S. Ser. No. 08/10958, filed
Jan. 29, 1993, pending the teachings of which are hereby
incorporated by reference herein.
One such polymerization process comprises:
contacting, optionally in a solvent, one or more .alpha.-olefins
with a catalyst according to the present invention comprising one
or more metal complexes according to the present invention in one
or more continuous stirred tank or tubular reactors, or in the
absence of solvent, optionally in one or more fluidized bed gas
phase reactors, connected in series or in parallel, and
recovering the resulting polymer.
In another such polymerization process, in one or more of the
foregoing reactors, one or more .alpha.-olefins are also contacted
with one or more catalyst compositions comprising one or more metal
complexes according to the present invention in admixture with a
catalyst composition comprising one or more homogeneous metallocene
complexes other than a complex according to the present invention,
said catalyst composition also comprising one or more cocatalyst
activators.
In yet another process an ethylene/.alpha.-olefin interpolymer
composition is prepared by:
(A) contacting ethylene and at least one other .alpha.-olefin under
polymerization conditions in the presence of a homogeneous catalyst
composition of the present invention comprising a metal complex of
the present invention with at least one of the aforementioned
activating cocatalysts in at least one reactor to produce a first
interpolymer or optionally a solution of a first interpolymer,
(B) contacting ethylene and at least one other .alpha.-olefin under
polymerization conditions at optionally a different, preferably a
higher, polymerization reaction temperature than used in step (A)
in the presence of a heterogeneous Ziegler catalyst in at least one
other reactor to produce a second interpolymer optionally in
solution, and
(C) combining the first interpolymer and second interpolymer to
form an ethylene/.alpha.-olefin interpolymer blend composition,
and
(D) recovering the ethylene/.alpha.-olefin interpolymer blend
composition.
Preferably the heterogeneous Ziegler catalyst comprises:
(i) a solid support component comprising magnesium halide, silica,
modified silica, alumina, aluminum phosphate, or a mixture thereof,
and
(ii) a transition metal component represented by the formula:
TrX".sub.u (X'").sub.v-u, or TrX".sub.u O(X'").sub.v-u-2
wherein:
Tr is a Group 4, 5, or 6 metal,
O is oxygen,
X" is halogen,
X'" is independently selected from hydrocarbyl, silyl,
hydrocarbyloxy or siloxy having up to 10 non-hydrogen atoms,
u is a number from 0 to 6 that is less than or equal to v, and
v is the formal oxidation number of Tr.
These polymerizations are generally carried out under solution
conditions to facilitate the intimate mixing of the two
polymer-containing streams. The foregoing technique allows for the
preparation of ethylene/.alpha.-olefin interpolymer compositions
having a broad range of molecular weight distributions and
composition distributions. Preferably, the heterogeneous catalyst
is also chosen from those catalysts which are capable of
efficiently producing the polymers under high temperatures,
especially, temperatures greater than or equal to 180.degree. C.
under solution process conditions.
In a still further embodiment, there is provided a process for
preparing an ethylene/.alpha.-olefin interpolymer composition,
comprising:
(A) polymerizing ethylene and at least one other .alpha.-olefin in
a solution process under suitable solution polymerization
temperatures and pressures in at least one reactor containing a
catalyst composition comprising the metal complex of the present
invention with at least one of the aforementioned activating
cocatalysts to produce a first interpolymer solution,
(B) passing the interpolymer solution of (A) into at least one
other reactor containing a heterogeneous Ziegler catalyst, in the
presence of ethylene and optionally one other .alpha.-olefin under
solution polymerization conditions to form a solution comprising
the ethylene/.alpha.-olefin interpolymer composition, and
(C) recovering the ethylene/.alpha.-olefin interpolymer
composition.
Preferably the heterogeneous Ziegler catalyst comprises:
(i) a solid support component comprising a magnesium halide, silica
or modified silica, including calcined silica, and
(ii) a transition metal component represented by the formula:
TrX".sub.u (X'").sub.v-u, or TrX".sub.u O(X'").sub.v-u-2
wherein:
Tr, X", X'", O, u, and v are as previously defined.
The foregoing technique also allows for the preparation of
ethylene/.alpha.-olefin interpolymer compositions having a broad
range of molecular weight distributions and composition
distributions. Particularly desirable .alpha.-olefins for use in
the foregoing processes are C.sub.3-8 .alpha.-olefins, most
desirably 1-octene.
The skilled artisan will appreciate that the invention disclosed
herein may be practiced in the absence of any component which has
not been specifically disclosed. The following examples are
provided as further illustration thereof and are not to be
construed as limiting. Unless stated to the contrary all parts and
percentages are expressed on a weight basis.
EXAMPLE 1
(N-t-butylamido)(dimethyl)(6,6-dimethyl.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)chloride
1. Preparation of
5,5-dimethyl-1,3-cyclohexadiene/3,3-dimethyl,-1,4-cyclohexadiene
isomeric mixture
In a glass flask under nitrogen atmosphere, 50.0 g (0.357 mol)
5,5-dimethyl-1,3-cyclohexanedione(dimmedone) was slurried in about
500 mL of diethyl ether. After cooling the slurry in an ice bath,
13 g (0.342 mol) of LiAlH.sub.4 was slowly added. The reaction
mixture was allowed to warm to room temperature and was stirred for
2 hours, after which 14 g (0.369 mol) of additional LiAlH.sub.4 was
added. The reaction mixture was refluxed for 2 hours, then stirred
overnight. Workup occurred as follows: After the reaction mixture
was cooled in an ice bath, 27 mL of water was slowly added,
followed by 27 mL of 15 weight percent, aqueous NaOH solution, then
81 mL of water. The resulting solids were filtered off and washed
with diethyl ether. The combined ether solutions were concentrated
by evaporation. To the resulting pale yellow product was added 10
mL of 9M aqueous H.sub.2 SO.sub.4. The product was collected after
distillation using a short path distillation column up to a pot
temperature of 145.degree. C. Additional H.sub.2 SO.sub.4 was added
and a second distillation was performed. After washing with 10
weight percent, aqueous Na.sub.2 CO.sub.3, then with water, the
product was dried with anhydrous MgSO.sub.4. The product was
fractionally distilled, with fractions boiling up to about
100.degree. C. being collected. The yield was 12 g. of the isomeric
mixture depicted as follows: ##STR10## 2. Preparation of potassium
6,6-dimethylcyclohexadienide
To 14.0 g (0.111 mol) of potassium t-amylate (KOC(CH.sub.3).sub.2
C.sub.2 H.sub.5) in 200 mL of pentane was added 44.4 mL of 2.5M
(0.111 mol) butyl lithium in hexane with formation of a small
amount of brownish insoluble material. To this was added 12.0
(0.111 mol) of the dimethylcyclohexadiene isomeric mixture. A
bright orange product resulted. After stirring overnight, the color
became brownish orange. The product was filtered, washed several
times with pentane, then dried under reduced pressure. The yield of
orange powder was 11.8 g, 72.7 percent.
3. Preparation of
(N-t-butylamino)(dimethyl)(4,4-dimethyl-2,5-cyclohexadien-1-yl)silane
To a solution of 5.46 g (32.9 mmol) of ClSi(CH.sub.3).sub.2
NHC(CH.sub.3).sub.3 (obtained according to the technique of
EP-A-563,365) in tetrahydrofuran(THF) was slowly added 4.50 g (30.8
mmol) of solid potassium 6,6-dimethylcyclohexadienide. After
stirring overnight, the reaction mixture was filtered and the
solvent was removed under reduced pressure. The residue was
extracted with pentane, the resulting slurry was filtered and the
solvent was removed from the filtrate. Purification by Kugelrohr
distillation gave 3.58 g of product, 49.0 percent yield. .sup.1 H
NMR (C.sub.6 D.sub.6) .delta.5.69 (d, 10.2 Hz, 2H), 5.45 (d, 9.9
Hz, 2H), 2.30 (s, 1H), 1.13 (s, 3H), 1.12 (s, 3H), 1.07 (s, 9H),
0.12 (s, 6H). The structure of the product is depicted as follows:
##STR11## 4. Preparation of
dilithium(N-t-butylamido)(dimethyl)(4,4-dimethyl-.eta..sup.5
-cyclohexadien-1-yl)silane
To 3.58 g (15.1 mmol) of
(N-t-butylamino)(dimethyl)(4,4-dimethyl-2,5-cyclohexadien-1-yl)silane
in 75 mL of diethyl ether was added 12.6 mL of 2.52M n-butyl
lithium in hexane. The resulting yellow reaction solution was
stirred for several days, during which time a large amount of
precipitate had formed. The reaction mixture was refluxed for
several hours, then it was filtered. The solid was washed with
hexane and then dried under reduced pressure. The yield of the pale
yellow powder was 2.01 g, 53.5 percent yield.
5. Preparation of
(N-t-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III)chloride
0.320 g of TiCl.sub.3 (THF).sub.3 (1.40 mmol) was dissolved in 25
mL of THF. To this solution 0.350 g of dilithium
((N-t-butylamino)(dimethyl)(4,4-dimethyl-1,3-cyclohexadien-1-yl)silane)
(1.40 mmol) was added and the solution stirred for 20 minutes. The
reaction mixture changed color indicating formation of the desired
product but recovery was not attempted. Instead, the product was
converted to the corresponding 2-(dimethylamino)benzyl complex in
Example 2.
EXAMPLE 2
(N-t-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(III) 2-(dimethylamino)benzyl
0.198 g of 2-dimethylaminobenzyl lithium (1.40 mmol) was added to
the reaction mixture of Example 1 and the solution was stirred for
20 minutes. After this time period the solvent was removed under
reduced pressure and the residue extracted with pentane and
filtered. The filtrate was concentrated and kept at -35.degree. C.
overnight to give 0.080 g (14 percent yield) of the desired
product. The structure of the resulting product is as follows:
##STR12## Polymerization
A two liter stirred reactor was charged with 800 g of toluene
solvent and 50 g of 1 -octene. The reactor was heated to
140.degree. C. and saturated with ethylene at 3.4 MPa (500 psi).
Catalyst and cocatalyst were mixed in a dry box by combining 0.2 mL
of a 0.005M toluene solution of
(N-t-butylamido)(dimethyl)(6,6-dimethyl-.eta..sup.5
-cyclohexadien-3-yl)silanetitanium(Ill) 2-(dimethylamino)benzyl
(1.0 .mu.mole) and 1.0 .mu.mole of ferrocenium
tetrakis(pentafluorophenyl)borate also in toluene. The resulting
solution was transferred to a catalyst addition tank and injected
into the reactor, The polymerization was allowed to proceed with
ethylene being added on demand. After 10 minutes the polymer
solution was removed from the reactor. A hindered phenol
antioxidant (Irganox.TM. 1010 available from Ciba Geigy Corp.), 100
mg, was added. Volatiles were removed under reduced pressure in an
oven at about 130.degree. C. for approximately 18 hours. Yield was
2.0 g of ethylene/1-octene copolymer.
EXAMPLE 3
(N-t-butylamido)(dimethyl)(1,1-dimethyl-2,3,4,9,10-.eta.-1,2-dihydronaphtha
len-4-yl)silanetitanium(III)chloride
1. Preparation of potassium 4,4-dimethyldihydronaphthalide
A mixture of 4,4-dimethyl-3,4-dihydronaphthalene and
4,4-dimethyl-1,4-dihydronaphthalene (83:17 ratio, 6.00 g, 37.9
mmol) was dissolved in approximately 200 mL of hexane in a 250 mL
flask. To the flask was added is potassium amylate (4.91 g, 38.9
mmol) followed by n-BuLi (16.1 mL, 2.48M, 39.8 mmol). Immediate
formation of an orange solid resulted. After stirring for 1 hour,
the slurry was filtered and the solid washed four times with 20 mL
of hexane each time. The solid was transferred to a flask which was
evacuated to remove any volatiles. The desired product was
recovered as a powdery orange solid. Yield was 6.91 g, 93
percent.
2. Preparation of
(dimethyl)(N-t-butylamino)(4,4-dimethyldihydronaphthalen-1-yl)silane
A 500 mL flask was charged with dimethyl(t-butylamino)chlorosilane
(ClSiMe.sub.2 NH.sup.t Bu) (5.81 g, 35.1 mmol) and approximately 80
mL of THF. A constant addition funnel was attached containing the
potassium 4,4-dimethyldihydronaphthalide complex of step 1 (4.00 g,
20.4 mmol) dissolved in about 120 mL of THF. The flask was cooled
to -78.degree. C. and the orange solution added dropwise over a 3
hour period. The bath was removed and the mixture allowed to warm
to 25.degree. C. during which the color changed from tan to yellow.
The solvent was removed under reduced pressure and the residue
triturated once with 80 mL of hexane. The residue was taken up in
hexane and filtered through Celite.TM. brand diatomaceous earth
filter aid. The solids were washed once with 20 mL of hexane and
the combined filtrates were concentrated. Stirring overnight under
reduced pressure resulted in a yellow oil. Yield was 4.72 g, 80
percent.
3. Preparation of
dilithium(dimethyl)(N-t-butylamido)(4,4-dimethyldihydronaphthalen-1-yl)sil
ane
A 250 mL flask was charged with the
(dimethyl)(N-t-butylamino)(4,4-dimethyldihydronaphthalenyl)silane
mixture of step 2 (4.72 g, 16.4 mmol) and 120 mL of diethylether.
To this solution was added sec-BuLi (25.9 mL, 1.3M, 33.6 mmol) in
small aliquots via syringe through a septum at 25.degree. C. The
yellow-orange mixture was stirred overnight. The reaction mixture
was filtered though Celite.TM. brand diatomaceous earth filter aid,
the ether was removed and the residue triturated with hexane three
times and discarded. The hexane was removed by evaporation and
diethylether was added. This mixture was stirred overnight during
which time a solid formed. The yellow solid flocculent material was
isolated by filtration and dried in vacuo. Yield was 0.66 g, 13
percent.
4.
(dimethyl)(N-t-butylamido)(1,1-dimethyl-2,3,4,9,10-.eta.-1,2-dihydronaphth
alen-4-yl)silane titanium(III)chloride
A 250 mL glass flask was charged with TiCl.sub.3 (THF).sub.3 (495
mg, 1.34 mmol) and 120 mL of THF. To this was added via pipet a THF
solution of dilithium
((N-t-butylamido)(dimethyl)(4,4-dimethyl-1,2,3,
9,10-.eta.-1,2-dihydronaphthalen-1-yl)silane) (400 mg, 1.34 mmol).
The solution turned brown opaque. PbCl.sub.2 (672 mg, 2.42 mmol)
was added as a solid. The mixture was stirred for 2 hours at
25.degree. C. and then filtered through Celite.TM. brand
diatomaceous earth filter aid to give a brown solution.
Concentration of the solution under reduced pressure and cooling to
-25.degree. C. produced brown crystals which were isolated via
filtration. Yield was 120 mg, 22 percent. ESR analysis showed the
product to be the above complex.
EXAMPLE 4
(N-t-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-1-yl)silanetitanium(III)chloride
1. Preparation of
(N-t-butylamido)(dimethyl)(2,4-dimethyl-.eta..sup.5
-pentadien-1-yl)silanetitanium(III)chloride(THF adduct)
A reaction mixture was formed by combining 0.862 g (2.77 mmol) of
dilithium
(N-t-butylamido)(dimethyl)(2,4-dimethyl-2,4-pentadien-1-yl)silane
and 1.35 g (3.63 mmol) of TiCl.sub.3.3THF in 50 mL of THF. After
stirring overnight, the solution was filtered, the solvent was
removed under reduced pressure, the residue was extracted with
pentane, the dark solution was filtered and then concentrated and
chilled in a -35.degree. C. freezer. The brown solid product was
isolated.
EXAMPLE 5
(Dimethyl)(N-t-butylamido)(diphenylmethyl)silanetitanium(III)chloride
Preparation of diphenylmethyl potassium
To a solution of 18.3 g (109 mmol) of diphenylmethane in 400 mL of
hexane were added 11.99 g (109 mmol) of potassium t-amylate. To the
resulting pale yellow solution were added 68.75 mL of 1.60M (110
mmol) butyl lithium. The thick, bright orange slurry was stirred
overnight. The solids were collected on a filter, washed three
times with 100 mL, then twice with 50 mL of hexane, then dried
under reduced pressure. The yield of bright orange powder was 18.23
g, 81.2 percent.
Preparation of (N-t-butylamino)(dimethyl)(diphenylmethyl)silane
To a solution of 4.1 g (24.7 mmol) of ClSiMe2NHCMe3 in 80 mL of THF
were added 3.735 g (18.1 mmol) of solid diphenylmethyl potassium.
The orange color of the diphenylmethyl potassium disappeared
instantly and precipitate formed rapidly. The reaction mixture was
stirred for several days. The solvent was removed under reduced
pressure and the residue was extracted with hexane and the solvent
was removed under reduced pressure. The yellow liquid product was
subjected to vacuum pumping to remove the excess ClSiMe.sub.2
NHCMe.sub.3. The yield was 4.786 g, 88.9 percent.
.sup.1 H NMR, (CDCl.sub.3) .delta.7.33-7.06 (br, m, 10H), 3.57 (s,
1H), 1.22 (s, 1H), 1.06 (s, 9H), 0.08 (s, 6H). .sup.13 C NMR,
(CDCl.sub.3) .delta.142.8, 128.9, 128.0, 124.8, 49.6, 47.4, 33.8,
1.3.
Preparation of
dilithium(N-t-butylamido)(dimethyl)(diphenylmethyl)silane
To a solution of 4.786 g (16.1 mmol) of
(N-t-butylamino)(dimethyl)(diphenylmethyl)silane in 50 mL of ether
were added 14.1 mL of 2.285M (32.2 mmol) of n-butyl lithium in
hexanes. There was vigorous gas evolution and the reaction solution
darkened to an orange-red color. The reaction mixture was stirred
overnight. The bright orange precipitate which had formed was
filtered off, washed with hexane, then dried under vacuum. The
yield of bright orange powder was 2.213 g, 44.5%. Additional butyl
lithium solution (2-3 mL) was added to the filtrate, which was then
stirred for several days. More precipitate gradually formed. It was
isolated as above to give 0.916 g additional product. Total yield
was 3.13 g, 62.9 percent.
Preparation of
(N-t-butylamido)(dimethyl)(diphenylmethyl)silanetitanium(III)chloride
Solid dilithium(N-t-butylamido)(dimethyl)(diphenylmethyl)silane
(0.712 g, 2.30 mmol) was mixed with 0.853 g (2.30 mmol) of solid
TiCl.sub.3.3THF in a flask to which 50 mL of THF was then added. A
color change in the solution was noted. The reaction product was
subsequently utilized to prepare
(N-t-butylamido)(dimethyl)(diphenylmethyl)silanetitanium(IV)dichloride
by metal center oxidation using PbCl.sub.2 oxidant which was
subsequently used for a polymerization reaction.
Polymerization
A two liter stirred reactor was charged with 750 g of Isopar E.TM.
solvent and 110 g of 1-octene. The reactor was heated to
140.degree. C. and saturated with ethylene at 3.4 MPa (500 psi).
Catalyst and cocatalyst were mixed in a dry box by combining 0.6 mL
of a 0.005M toluene solution of
(N-t-butylamido)(dimethyl)(diphenylmethyl)silanetitanium(IV)dichloride
(3.0 .mu.mole) and 2.0 mL of a 1.5M toluene solution of
methylalumoxane (3000 .mu.mole). The resulting solution was
transferred to a catalyst addition tank and injected into the
reactor. The polymerization was allowed to proceed with ethylene
being added on demand. After 10 minutes the polymer solution was
removed from the reactor. A hindered phenol antioxidant
(Irganox.TM. 1010 available from Ciba Geigy Corp.), 100 mg, was
added. Volatiles were removed under reduced pressure in an oven at
about 130.degree. C. for approximately 18 hours. Yield was 1.1 g of
ethylene/1-octene copolymer.
* * * * *